2,2,3-Trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondary alkanols, alkanones, cycloalkanols and cycloalkanones, organoleptic uses thereof in perfume compositions, colognes and perfumed articles and process for producing same

ABSTRACT

Described are perfume and fragrance compositions and perfumed articles including soaps, detergents, powders as well as colognes containing 2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondary alkanols, alkanones, cycloalkanols and cycloalkanones having the generic structure: ##STR1## wherein one of the lines +++++ is a carbon-carbon double bond and the other of the lines +++++ is a carbon-carbon single bond; wherein X is carbinol having the structure: ##STR2## or carbonyl having the structure ##STR3## wherein A&#39; is hydrogen, CH 3 , C 2  H 5  or --CH 2  --; wherein B&#39; is hydrogen, CH 3 , C 2  H 5  or --CH 2  --; where n is 0, 1 or 2; wherein each of the dashed lines are the same and each represents a carbon-carbon single bond or no bond; wherein A&#39; and B&#39; are both --CH 2  -- when n is 1 or 2 and the dashed line is a carbon-carbon single bond or A&#39; is hydrogen and B&#39; is C 2  H 5  or CH 3  or both A&#39; and B&#39; are each CH 3  or A&#39; is C 2  H 5  and B&#39; is CH 3  when n is 0 and the dashed line represents no bond, which imparts thereto rich, musky, cedar woody, sandalwood, sweet, floral, ionone-like, soft-fruity (apricot), green and earthy aromas with resinous topnotes and nutty oily nuances. Also described is a process for preparing such compounds according to the reaction schemes: ##STR4## wherein the lines +++++ A&#39;, B&#39;, the dashed lines and n are as defined above wherein M is alkaline metal.

This is a divisional of application Ser. No. 932,677, filed Aug. 10,1978 now U.S. Pat. No. 4,173,585.

BACKGROUND OF THE INVENTION

There is a continuing search for materials having desirable fragranceproperties. Such materials are used either to replace costly naturalmaterials or to provide new fragrances of perfumed types which have notheretofore been available. Especially desirable qualities for substanceshaving interesting fragrances such as sandalwood-type fragrances arestability and persistence, paticularly in a wide variety of perfumedarticles (e.g. soaps, detergents and powders) perfumed compositions andcolognes, ease of manufacture and intensity of aroma.

Furthermore, according to Guenther [E. Guenther, "The Essential Oils",Vol. V. page 173, D. Van Nostrand Co., Inc., New York (1952)], EastIndian sandalwood oil "has been perhaps one of the most preciousperfumery materials from antiquity down to modern times, and itspopularity has shown no signs of waning." This oil is widely used inperfumery, and would be even more widely used except for its limitedsupply and high cost.

As is well known, a need exists for synthetic substances which can beused as sandalwood substitutes or extenders. It would be most desirableto be able to synthetically provide the major odorant compounds of thenatural sandalwood oil, i.e. alpha-santalol and beta-santalol, but nocommercially feasible route to these chemicals is known at this time.

It would be even more desirable to provide a synthetic compound whichwould have many of the desirable odor qualities of a fine East Indiansandalwood oil, yet not have the potentially labile primary allylicalcohol group present in the natural santalols. A compound which wouldbe more resistant to acidic or oxidative decomposition as well as beingbase stable could be even more versatile than sandalwood oil itself.

There is no obvious explanation why only slight chemical changes shouldhave such a dramatic effect on odor intensity other than to invoke thegeneral unreliability of odor structure relationships. Why the additionor removal of a methyl group, the removal of a double bond or the meremoving of a methyl group would essentially destroy more than 90% of theodor intensity rather than merely cause subtle odor differencescomparable to the subtle chemical differences cannot be explained by anytheoretical concepts in the known art.

U.S. Pat. No. 4,052,341, issued on Oct. 4, 1977 provides a sandalwoodtype aroma imparting material having one of the structures:

                  TABLE I                                                         ______________________________________                                        Name                Structure                                                 ______________________________________                                        3-Methyl-5-(2,2,3- trimethylcyclopent-3- en-1-yl)pentan-2-ol                                       ##STR5##                                                 3-Methyl-5-(2,2,3- trimethylcyclopentan-1- yl)pentan-2-ol                                          ##STR6##                                                 5-(2,2,3-Trimethyl- cyclopent-3-en-1-yl) pentan-2-ol                                               ##STR7##                                                 6-(2,2,3-Trimethyl- cyclopent-3-en-1-yl) hexan-3-ol                                                ##STR8##                                                 4-Methyl-6-(2,2,3- trimethylcyclopent-3- en-1-yl)hexan-3-ol                                        ##STR9##                                                 3-Ethyl-5-(2,2,3- trimethylcyclopent- 3-en-1-yl)pentan-2-ol                                        ##STR10##                                                3-Methyl-5-(2,3,3- trimethylcyclopent-3- en-1-(R)-yl)pentan-2-ol                                   ##STR11##                                                3-Methyl-5-(2,2,3- trimethylcyclopent- 3-en-1-(S)-yl)pentan-2-ol                                   ##STR12##                                                3-Methyl-5-(2,2,3- trimethylcyclopent- 3-en-l-yl)pent-3-en-2-ol                                    ##STR13##                                                ______________________________________                                    

These materials are produced according to the reaction schemes:

                                      TABLE II                                    __________________________________________________________________________     ##STR14##                                                                     ##STR15##                                                                     ##STR16##                                                                    __________________________________________________________________________     (a) R.sub.1 = H.sub.2 CH.sub.3 C.sub.2 H.sub.5                                  R.sub.2 = H.sub.1 CH.sub.3                                             

East Germany Pat. No. 68,936 discloses for use in the sandalwood area acompound having the structure: ##STR17## Furthermore, Chemical AbstractsVolume 72, 125008b sets forth a genus for the East German Pat. No.68,936 encompassing the following group of compounds: ##STR18## whereinR═CH₂ OH, CHCH₃ OH and R¹ ═H,CH₃ or C₂ H₅.

The processes of our invention using the zinc acetate catalyst provide ahighly efficient advantageous, unobvious route for a number of theaforementioned compounds and in addition provide certain novel compoundsheretofore unavailable having the generic structure: ##STR19## whereinone of the lines ++++ is a carbon-carbon single bond and the other ofthe lines ++++ is a carbon-carbon double bond and wherein X is one ofthe moieties ##STR20## and these compounds have unobvious and unexpectedproperties insofar as their perfumery properties are concerned.

The use in zinc acetate in carrying out such reactions has heretoforebeen unknown and is not obvious from the teachings of the prior art.Thus, Houben-Weyl, "Methoden der organischen Chemie", volume 7/1, pages77 et seq. and "Organic Reactions", volume 16, pages 27 to 47, 69 to 78and 177 et seq. disclose the fact that aldehydes and ketones can beconverted to α,β-unsaturated ketones. Temperatures of from 5° C. up to100° C. are preferred for this aldol condensation ("Organic Reactions,"loc. cit., page 77). The numerous catalysts used in these methods, forexample alkali and alkaline earth metal hydroxides, organic bases,alkali metal salts and alcoholates promote auto-condensation of thealdehydes and ketones and therefore cause the formation of large amountsof by-products in most cases.

Furthermore, the U.S. Pat. No. 4,005,147 discloses the production ofalpha,beta-unsaturated ketones by reacting in the liquid phase analdehyde with a ketone in the presence of a catalyst consistingessentially of zinc oxide.

It is furthermore known from U.S. Pat. No. 2,549,508 that aldehydes andketones can be converted into unsaturated ketones of high molecularweight in the gas phase at temperatures of from 500° to 1000° C. in thepresence of a catalyst consisting essentially of zinc oxide and from 1to 15% by weight of zirconium oxide. In this process however only lowconversions and low yields are achieved. Moreover high expenditure forequipment is required for reactions in the presence of hydrogen at thesaid temperatures for safety reasons. Moreover cracking processes takeplace at the surface of the catalyst in such reactions and these have anegative effect on the life of the catalyst.

The reaction of two identical or different aldehydes or ketones in theliquid phase at elevated temperature and in the presence of a catalyst(obtained by calcining a mixture of molybdenum oxide, magnesium oxidewith or without zinc oxide or compounds of these metals) to fromalpha,beta-unsaturated aldehydes or ketones is known from German Pat.No. 1,203,243.

According to the method described in the said patent good conversionsand very good yields of alpha,beta-unsaturated aldehydes are obtained inthe condensation of aldehydes with one another, particularly in thecondensation of n-butyraldehyde or 2-ethylhexenal.

The process of German Pat. No. 1,203,243 is not so suitable for thereaction of aldehydes with ketones to form alpha,beta-unsaturatedketones, considerably lower conversions and selectivities beingachieved. This is particularly noticeable when not only isobutyraldehyde(i.e., and aldehyde which does not undergo autocondensation) is reactedwith a ketone by the method of the said German patent, but alsoaldehydes are used which readily undergo autocondensation, as forexample 3,3-dimethylacrolein and citral.

Nothing in the prior art, however, implies the process of our inventionusing zinc acetate catalyst whereby2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondaryalkanols, alkanones, cycloalkanols and cycloalkanones may be produced ina convenient, sufficient and economical manner.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the product produced according to theprocess of Example IA having the structure: ##STR21##

FIG. 2 is a GLC profile for a refined form of the compound having thestructure: ##STR22## resulting from fractionation of the reaction mass.

FIG. 3 is the infrared spectrum for the compound having the structure:##STR23## produced according to the process of Example IA.

FIG. 4 is the GLC profile for the product produced according to ExampleIB which is a mixture defined by the structure: ##STR24## wherein eitherR₁ or R₂ is methyl and the other is hydrogen and one of the dashed linesis a carbon-carbon single bond and the other of the dashed lines is acarbon-carbon double bond.

FIG. 5 is the NMR spectrum for the product produced according to ExampleIB containing compounds having the structures: ##STR25##

FIG. 6 is the infrared spectrum for the product produced according toExample IB containing compounds having the structures: ##STR26##

FIG. 7 is the NMR spectrum for the product produced according to ExampleIB having compounds having the structures: ##STR27##

FIG. 8 is the infrared spectrum of the reaction product of Example IBcontaining compounds having the structures: ##STR28##

FIG. 9 is the NMR spectrum for the reaction product produced accordingto Example IB having compounds having the structures: ##STR29##

FIG. 10 is the infrared spectrum for the reaction product producedaccording to Example IB having compounds having the structures:##STR30##

FIG. 11 is the NMR spectrum for the reaction product of Example IBhaving structures: ##STR31##

FIG. 12 is the GLC profile for the product produced according to theprocess of Example IC having a mixture of compounds contained thereinhaving the generic structure: ##STR32## (R₁ or R₂ is methyl and theother of R₁ or R₂ is hydrogen and one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond.

FIG. 13 is the NMR spectrum for the reaction product of Example IC, peak"A" of the GLC profile of FIG. 12.

FIG. 14 is the NMR spectrum for the reaction product of Example IC, peak"B" of the GLC profile of FIG. 12.

FIG. 15 is the NMR spectrum for the reaction product of Example IC, peak"C" of the GLC profile of FIG. 12.

FIG. 16 is the infrared spectrum for the reaction product of Example IC,peak "C" of the GLC profile of FIG. 12.

FIG. 17 is the NMR spectrum for the reaction product of Example IC, peak"D" of the GLC profile of FIG. 12.

FIG. 18 is the infrared spectrum for the reaction product of Example IC,peak "D" of the GLC profile of FIG. 12.

FIG. 19 is the NMR spectrum for the reaction product of Example IC, peak"E" of the GLC profile of FIG. 12.

FIG. 20 is the infrared spectrum for the reaction product of Example IC,peak "E" of the GLC profile of FIG. 12.

FIG. 21 is the NMR spectrum for the reaction product of Example IC, peak"F" of the GLC profile of FIG. 12.

FIG. 22 is the infrared spectrum for the reaction product of Example IC,peak "F" of the GLC profile of FIG. 12.

FIG. 23 is the GLC profile for the reaction product of Example IIAconsisting of compounds having the structures: ##STR33##

FIG. 24 is the GLC profile for fraction 3 resulting from the fractionaldistillation of the reaction product of Example IIA which containscompounds having the structures: ##STR34##

FIG. 25 is the NMR spectrum for fraction 3 resulting from the fractionaldistillation of the reaction product of Example IIA having the compoundshaving the structures: ##STR35##

FIG. 26 is the GLC profile for the reaction product of Example IIBhaving the compounds having the structures: ##STR36##

FIG. 27 is the NMR spectrum for fraction 2 resulting from a fractionaldistillation of the reaction product of Example IIB, having compoundshaving the structures: ##STR37##

FIG. 28 is the NMR spectrum for peak "A" of the reaction product ofExample IIIA containing compounds having the structures: ##STR38##

FIG. 29 is the infrared spectrum for the reaction product of ExampleIIIA, peak "A" containing compounds having the structures: ##STR39##

FIG. 30 is the NMR spectrum for peak "B" of the reaction product ofExample IIIA containing compounds having the structures: ##STR40##

FIG. 31 is the infrared spectrum for peak "B" of the reaction product ofExample IIIA containing compounds having the structures: ##STR41##

FIG. 32 is the NMR spectrum for peak "A" of the reaction productproduced according to Example IIIB containing compounds having thestructures: ##STR42##

FIG. 33 is the NMR spectrum for peak "B" of the reaction product ofExample IIIB containing compounds having the structures: ##STR43##

FIG. 34 is the infrared spectrum for peak "B" of the reaction productproduced according to Example IIIB containing compounds having thestructures: ##STR44##

FIG. 35 is the GLC profile for bulked fractions 4-11 produced accordingto Example IVA wherein the two major peaks represent compounds havingthe structures: ##STR45##

FIG. 36 is the NMR spectrum for Peak A of the reaction product producedaccording to Example IVA containing compounds having the structures:##STR46##

FIG. 37 is the infrared spectrum for peak A of the reaction productproduced according to Example IVA.

FIG. 38 is the NMR spectrum for peak B of the reaction product producedaccording to Example IVA.

FIG. 39 is the infrared spectrum for peak B of the reaction productproduced according to Example IVA containing compounds having thestructures: ##STR47##

FIG. 40 is the GLC profile for the reaction product produced accordingto Example IVB wherein peaks A and B are four compounds having thestructures: ##STR48## Peak C is for a compound having the structure:##STR49## and peak D is for compounds having the structures: ##STR50##

FIG. 41 is the NMR spectrum for peak D produced according to Example IVBcontaining compounds having the structures: ##STR51##

FIG. 42 is the NMR spectrum for the reaction product produced accordingto Example VA containing compounds having the structures: ##STR52##

FIG. 43 is the infrared spectrum for the product produced according toExample VA containing compounds having the structures: ##STR53##

FIG. 44 is the NMR spectrum for the reaction product produced accordingto Example IVB containing compounds having the structures: ##STR54##

FIG. 45 is the infrared spectrum for the reaction product producedaccording to Example VB containing compounds having the structures:##STR55##

THE INVENTION

The invention comprises a novel process for preparing chemicals usefulin formulating perfume compositions, perfumed articles and colognes,which chemicals have the generic structure: ##STR56## wherein one of thelines +++++ is a carbon-carbon double bond and the other of the lines+++++ is a carbon-carbon single bond; wherein X is carbinol having thestructure: ##STR57## or carbonyl having the structure: ##STR58## whereinA' is one of hydrogen, CH₃, C₂ H₅ or --CH₂ --; wherein B' is hydrogen,CH₃, C₂ H₅ or --CH₂ --; wherein n=0, 1 or 2; wherein each of the dashedlines are the same and each represents a single bond or no bond; whereinA' and B' are each --CH₂ -- when n=1 or n=2 and the dashed linerepresents a single bond; or A' is hydrogen and B' is C₂ H₅ or CH₃ or A'is CH₃ and B' is CH₃ or C₂ H₅ when n=0 and each of the dashed linesrepresents no bond, the process comprising the first or both of thefollowing reaction schemes: ##STR59## wherein M represents alkalinemetal. The invention also comprises certain novel compounds, novelperfume compositions, novel perfumed articles and novel colognesprepared according to the above process and having the genericstructure: ##STR60## wherein one of the lines ++++ represents acarbon-carbon bond and the other of the lines ++++ represents acarbon-carbon double bond; and wherein X represents carbonyl having thestructure: ##STR61## or carbinol having the structure: ##STR62##

The specific embodiments of the foregoing invention are describedhereinafter by way of example in accordance with which it is nowpreferred to practice the invention.

The 2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondaryalkanols, alkanones, cycloalkanols and cycloalkanones of our inventionas defined by the structure: ##STR63## are obtained by first carryingout an "aldol" condensation of campholenic aldehyde with an acyclicketone containing three or four carbon atoms or a cyclic ketonecontaining six carbon atoms in the presence of zinc acetate therebyforming a mixture of isomers of ketones wherein in the above genericstructure X is carbonyl having the structure: ##STR64## This reactionmay be generically illustrated by the following reaction scheme:##STR65## ps The campholenic aldehyde itself may be prepared by means oftreatment of alpha pinene epoxide with Lewis acids, such as zinc bromideand zinc chloride thereby causing a rearrangement according to thereaction scheme: More specifically, the first step of the process of ourinvention may be specifically illustrated by the following reactionschemes: ##STR66## wherein either of R₁ or R₂ is methyl and the other ofR₁ or R₂ is hydrogen and one of the dashed lines is a carbon-carbondouble bond and the other of the dashed lines is a carbon-carbon singlebond; ##STR67## wherein one of the dashed lines is a carbon-carbondouble bond and the other of the dashed lines is a carbon-carbon singlebond; and ##STR68##

The resulting ketone mixture may then be subjected to reduction usingalkaline metal borohydrides such as sodium borohydride to produce amixture of alcohols or the resulting mixture may be used as in perfumeryfor perfume mixtures or perfumed articles or colognes or the resultingmixture of ketones may be separated into their respective componentisomers and used as is or individually reduced using alkaline metalborohydrides.

In the event that it is desired to reduce said ketone mixture or saidindividual ketones to the corresponding mixture of alcohols orindividual alcohols, the reaction utilized may be illustrated by thefollowing reaction scheme: ##STR69## wherein one of the lines ++++++ isa carbon-carbon double bond and the other of the line ++++++ is acarbon-carbon single bond; wherein A' is hydrogen, methyl or --CH₂ --;wherein B' is hydrogen, CH₃, C₂ H₅ or --CH₂ --; where n is 0, 1 or 2;wherein each of the dashed lines are the same and each represents asingle bond or no bond at all; wherein A' and B' each represent --CH₂ --when n=1 or n=2 and each of the dashed lines represents a single bond;or A' is hydrogen and B' is C₂ H₅ or CH₃ or A' is CH₃ and B' is CH₃ orC₂ H₅ when n=0 and the dashed line represents no bond at all. Morespecifically, the reduction reaction may be illustrated by the followingreaction sequences: ##STR70## wherein one of R₁ or R₂ is methyl and theother of R₁ or R₂ is hydrogen and wherein one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond; ##STR71## wherein one of the dashed lines isa carbon-carbon single bond and the other of the dashed lines is acarbon-carbon double bond; and ##STR72## wherein M is alkaline metalsuch as sodium or potassium.

In carrying out the first step of the process of our reaction formingketones by means of reacting campholenic aldehyde with C₃ or C₄ ketone,the catalyst contemplated herein are zinc acetate and zinc acetatedihydrate. The zinc acetate dihydrate is preferred since it gives riseto a higher yield of desired product useful in perfumery, perfumedarticles and colognes.

The mole ratio of catalyst: ketone reactant is in the range of 0.05 upto 1.0 mole per mole of ketone reactant; preferably about 0.2 moles ofcatalyst per mole of ketone reactant.

The range of mole ratio of ketone reactant: campholenic aldehydereactant is in the range of from about 10:1 to about 1:1, with apreferred mole ratio range of ketone: campholenic aldehyde of 3:1 up to5:1.

The temperature of the aldol condensation reaction using the zincacetate dihydrate is between 100° C. and 250° C., preferably in therange of from about 130° C. up to about 200° C.

Although atmospheric pressure may be used, it is preferred to operatethe aldol condensation reaction at pressures in the range of from about100 psig up to about 400 psig depending on the scale and size of theautoclave used and correspondingly it is preferred to carry out thereaction in an autoclave suited for pressures up to about 500 psig.

The reaction may be monitored using vapor phase chromotographytechniques. At the end of the reaction the reaction mass is "worked up"using standard techniques, for example, filtration, neutralization,drying and fractional distillation. The individual isomers may be alsoseparated using preparative GLC, if desired. Usually if the ketonemixture is to be further reacted such separation is not commerciallyfeasible.

The step of reducing the ketone(s) to the corresponding alcohol withoutreduction of double bonds contained in cyclopentenyl ring or in thealkenyl side-chain is carried out using an alkaline metal borohydridecatalyst, for example, sodium borohydride or potassium borohydride.

The reaction also is to take place in he presence of an inert solventsuch as anhydrous methanol, anhydrous ethanol or anhydrousisopropylalcohol. The temperature of reaction is between 0° C. and 40°C.; preferably between 15° C. and 30° C. The most convenient pressure touse is one atmosphere, however, higher pressures may be used withoutreduction in yield or conversion.

The concentration of alkaline metal borohydride in the reaction mass mayvary from 10 grams per liter up to 200 grams per liter with a preferredrange of catalyst concentration of between 40 and 80 grams per liter ofalkaline metal borohydride.

The concentration of ketone reactant in the reaction mass may vary from500 grams per liter up to 1000 grams per liter with a preferred range offrom 700 up to 800 grams per liter.

The ratio of alkaline metal borohydride catalyst to ketone reactant mayvary from 0.05:1 up to 0.3:1 with a preferred range of weight ratios ofcatalyst: ketone reactant being from 0.08:1 up to about 0.12:1.

The reduction reaction may be monitored using GLC techniques, ifdesired. At the end of the reaction, the reaction mass is "worked up"using standard physical "work up" procedures including extraction,neutralization, drying and fractional distillation. Furthermore, ifdesired, a fractionally distilled material which conveniently is amixture of isomers of alcohols, may be further separated usingpreparative GLC techniques.

Specific examples of 2,23-trimethyl-3-cyclopenten-1-ylalkenyl andalkylidene secondary alkanols, alkanones, cycloalkanols andcycloalkanones produced using the aforementioned process and theirperfumery properties are as follows, as set forth in Table II below.

                  TABLE II                                                        ______________________________________                                        Structure of 2,2,3-trimethyl-                                                 3-cyclopenten-1-ylalkenyl and                                                 alkylidene secondary alkanols,                                                alkanones, cycloalkanols and                                                  cycloalkanones in mixtures                                                                      Aroma of Mixtures                                           ______________________________________                                        Mixture of compounds each of                                                                    At 10% in food grade ethanol,                               which is defined within the                                                                     a sweet, woody, (sandal-                                    genus having the structure:                                                                     wood) ionone-like aroma                                                       with green, melony nuances.                                  ##STR73##                                                                    wherein one of the dashed lines                                               is a carbon-carbon single bond                                                and the other of the dashed lines                                             is a carbon-carbon double bond                                                and wherein one of R.sub.1 or R.sub.2 is                                      methyl and the other of R.sub.1 or R.sub.2                                    is hydrogen.                                                                  Mixture of compounds defined                                                                    A powerful sandalwood note,                                 by the generic structure:                                                                       with nutty, oily nuances                                                      having intense musky                                                          nuances also.                                                ##STR74##                                                                    wherein one of the dashed                                                     lines is a carbon-carbon                                                      single bond and the other of                                                  the dashed lines is a carbon-                                                 carbon double bond and one of                                                 R.sub.1 or R.sub.2 is methyl and the other                                    of R.sub.1 or R.sub.2 is hydrogen.                                            Mixture of compounds having the                                                                 A cedarwood, sandal-                                        structures:       wood sweet aroma                                             ##STR75##                                                                     ##STR76##                                                                     ##STR77##                                                                    Mixture of compounds having the                                                                 At 10% in foodgrade                                         structures:       ethanol, a sweet                                                              floral, ionone-                                                               like soft fruity                                                              (apricot) aroma with                                                          nutty, woody and                                                              slight sandalwoody                                                            nuances                                                      ##STR78##                                                                     ##STR79##                                                                     ##STR80##                                                                     ##STR81##                                                                    Mixture of compounds having the                                                                 A sandalwoody aroma with                                    structures:       resinous topnote.                                            ##STR82##                                                                     ##STR83##                                                                     ##STR84##                                                                     ##STR85##                                                                    Compound defined by the                                                                         A fruity, ionony, green,                                    structure:        somewhat buttery aroma                                       ##STR86##                                                                    Compound defined by the                                                                         A floral ionone, violets-                                   structure:        like aroma with a slightly                                                    fatty rue oil note.                                          ##STR87##                                                                    Mixture of compounds having the                                                                 A low-keyed woody, amber                                    structures:       aroma with a slight spiciness                                ##STR88##                                                                     ##STR89##                                                                     ##STR90##                                                                    Mixture of compounds having                                                                     A low-keyed woody, sandle-                                  the structures:   wood-like note with "cycla-                                                   mal/lilial" type character.                                  ##STR91##                                                                     ##STR92##                                                                     ##STR93##                                                                    ______________________________________                                    

One or more of the above-mentioned2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondaryalkanols, alkanones, cycloalkanols and cycloalkanones or mixtures of2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondaryalkanols, alkanones, cycloalkanols and cycloalkanones defined accordingto the generic structure: ##STR94## wherein one of the lines ++++++ is acarbon-carbon double bond and the other of the lines ++++++ is acarbon-carbon single bond; wherein X is carbinol having the structure:##STR95## or carbonyl having the structure: ##STR96## wherein A' ishydrogen, CH₃ or --CH₂ --; wherein B' is H, CH₃, C₂ H₅ or --CH₂ --;wherein n=0 or 2; wherein the dashed line is a carbon-carbon single bondor represents no bond; wherein when A' and B' are each --CH₂ --, n=2 andthe dashed lines are each carbon-carbon single bonds; or when A' ishydrogen and B' is C₂ H₅ or CH₃, or when A' is methyl and B' is methylor C₂ H₅, n=0 and the dashed line represents no bond is an olfactoryagent and can be incorporated into a wide variety of compositions eachof which will be enhanced or augmented by it rich, musky and/or cedarwoody and/or sandalwood and/or green, earthy and/or ionone-like and/orsweet, fruity and/or sweet floral notes. The2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondaryalkanols, alkanones, cycloalkanols and cycloalkanones can be added toperfume compostions as pure compounds or can be added to mixtures ofmaterials in fragrances imparting compositions to provide a desiredfragrance character to a finished perfume material. The perfume andfragrance compositions obtained according to our invention are suitablein a wide variety of perfume articles and can be also used to enhance,modify or reenforce natural fragrance materials. It will thus beappreciated that the 2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl andalkylidene secondary alkanols, alkanones, cycloalkanols andcycloalkanones of our invention is (are) useful as olfactory agent(s)and fragrance(s).

The term "perfume composition" is used herein to mean a mixture ofcompounds including, for example, natural oils, synthetic oils, alcoholsother than those covered by the alcohols produced according to thisinvention, aldehydes, alcohols other than those alcohols producedaccording to the processes of our invention, ketones other than thoseketones produced according to the processes of our invention, esters,lactones, nitriles and frequently hydrocarbons which are admixed so thatthe combined odors of the individual components produce a pleasant ordesired fragrance. Such perfume compositions usually contain (a) themain note or the "bouquet" or foundation-stone of the composition; (b)modifiers which round-off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation, and substances whichretard evaporation; and (d) top-notes which are usually low-boilingfresh-smelling materials. Such perfume compositions of our ivnention canbe used in conjunction with carriers, vehicles, solvents, dispersants,emulsifiers, surface-active agents, aerosol propellants and the like.

In perfume compositions the individual components contribute theirparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, one or more of the 2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl andalkylidene secondary alkanols, alkanones, cycloalkanols andcycloalkanones of our invention can be used to alter, augment, modify orenhance the aroma characteristics of a perfume composition or a perfumedarticle, for example, by highlighting or moderating the olfactoryreaction contributed by another ingredient of the composition.

The amount of one or more of the2,2,3-trimethyl-3-cyclopenten-1-ylalkenyl and alkylidene secondaryalkanols, alkanones, cycloalkanols and cycloalkanones of our inventionwhich will be effective in perfume compositions depends upon manyfactors, including the other ingredients, their amounts and the effectswhich are desired. It has been found that perfume compositionscontaining as much as 40% or as little as 0.1 ppm (0.00001%) by weightof the mixtures or compounds produced according to the process of ourinvention or the mixtures or compounds of this invention or even lesscan be used to impart a rich musky and/or cedarwoody and/or sandalwoodand/or green earthy and/or ionone-like and/or sweet floral aroma tosoaps, cosmetics and other products. The amount employed will dependupon considerations of cost, nature of the end product, the effectdesired in the finished product and the particular fragrance sought.

One or more of the 2,2,3-trimethyl-3-cyclopenten-1-yl-alkenyl andalkylidene secondary alkanols, alkanones, cycloalkanols andcycloalkanones of our invention as disclosed herein can be used alone,in a fragrance modifying composition or in a perfume composition as anolfactory component in detergents (anionic detergents, cationicdetergents and nonionic detergents) and soaps; space deodorants;perfumes; colognes, bath preparations such as bath oil, bath salts; hairpreparations such as lacquers, brilliantines, pomades, and shampoos;cosmetic preparations such as cremes, deodorants, hand lotions, sunscreens; powders such as talcs, dusting powders, face powders and thelike. When one or more of the 2,2,3-trimethyl-3-cyclopenten-1-ylalkenyland alkylidene secondary alkanols, alkanones, cycloalkanols andcycloalkanones of our invention is used in perfumed articles such as theforegoing, it can be used in amounts of 0.5 ppm (0.00005%) or lower.Generally it is preferred not to use less than about 0.2% no more thanabout 25% in the finished perfumed article, since the use of too muchwill tend unbalance the total aroma and will needlessly raise the costof the article.

The following examples serve to illustrate embodiments of the inventionas it is now preferred to practice it. It will be understood that theseexamples are illustrative and the invention is to be restricted theretoonly as indicated in the appended claims.

EXAMPLE IA PREPARATION OF CAMPHOLENIC ALDEHYDE

Reaction ##STR97##

Into a 5 liter flask reaction vessel equipped with reflux condenserthermometer stirrer and heating mantle and addition funnel is added 15.9grams of zinc metal (0.21 moles) and 86 ml tetrahydrofuran. 40.3 gramsof 1,2-dibromoethane is added at reflux dropwise over a period of 1 hour(reflux temperature=73° C.). After the addition is completed, thereaction mass is stirred at reflux for a period of 3 hours (76° C.). 430ml toluene is then added and the reaction system is set up fortetrahydrofuran/toluene recovery.

The reaction mass is then transferred to a 5 liter flask and 2145 gramsof toluene are added. Alpha-pinene epoxide (1086 grams, 7.1 moles) isthen added over a period of 1 hour while maintaining the reaction masstemperature below 53° C. using dry-ice/isopropanol bath in order tocontrol exotherm. The reaction mass is then stirred for an additional 2hours after addition is complete. The reaction mass is then intimatelyadmixed with a 10% acetic acid solution to a pH of 4.3 followed byneutralization with sodium bicarbonate and sodium chloride solutions.The toluene is then recovered and the reaction mass crude material is"rush over" distilled whereby 785.3 grams of product is collected.(Chemical yield=74%). The rush over distillation fractions are collectedusing a 2 inch rush over column packed with saddle stones yielding thefollowing fractions:

    ______________________________________                                             Vapor     Liquid    Vac    Weight Product                                Fr.  Temp(°C.)                                                                        Temp(°C.)                                                                        (mmHg) (g)    (g)                                    ______________________________________                                        1    35-46      51-100   90     2284    62                                    2    46-83     86-96     10     188    156                                    3    83-84      96-153   10     549    510                                    4    84-90     153-202   10      50     40                                    ______________________________________                                    

FIG. 1 is the GLC profile for the reaction product of this example priorto fractional distillation.

FIG. 2 is the GLC profile of fraction 3 subsequent to the rush overdistillation which includes campholenic aldehyde.

FIG. 3 is the infrared spectrum for campholenic aldehyde producedaccording to this example.

EXAMPLE IB PREPARATION OF MIXTURE OF3-METHYL-5-(2,2,3-TRIMETHYL-3-CYCLOPENTENE-1-YL)-3(OR 4)-PENTENE-2-ONEAND 6-(2,2,3-TRIMETHYL-3-CYCLOPENTENE-1-YL)-4(OR 5)-HEXENE-3-ONE

Reaction ##STR98## wherein one of R₁ or R₂ is methyl and the other of R₁or R₂ is hydrogen and one of the dashed lines is a carbon-carbon doublebond and the other of the dashed lines is a carbon-carbon single bond.

Into a 2 liter autoclave are charged 152 grams of2,2,3-trimethyl-3-cyclopetene-1-yl acetaldehyde produced according toexample IA, 220 grams of methyl ethyl ketone and 44 grams of zincacetate dihydrate. The reaction mixture is heated at 180° C. for aperiod of 10 hours. After cooling, the reaction mixture is filtered toremove the zinc acetate dihydrate catalyst and washed with 200 ml ofsaturated sodium chloride solution. Distillation at 4.0 mmHg pressureyields 172 grams of crude product. Redistillation at 3.0 mmHg pressuregives 142 grams of pure product, boiling point 115°-122° C. at 3.0 mmHgpressure.

The fractionation data resulting from the redistillation is as follows:

    ______________________________________                                             Vapor      Liquid     Vac.   Fraction                                    No.  Temp(°C.)                                                                         Temp (°C.)                                                                        mmHg   Weight (grams)                              ______________________________________                                        1    50-64      111-120    3      11.1                                        2     64-115    120-139    3      20.7                                        3    115        139        3      20.5                                        4    115-116    139        3      17.2                                        5    116-118    139        3      18.9                                        6    118        139-141    3      21.8                                        7    118-120    141-143    3      19.3                                        8    120-122    143-150    3      19.8                                        9    122        150-175    3      10.3                                        ______________________________________                                    

FIG. 4 is the GLC profile for the reaction product (conditions: 10'×1/4inch carbowax column programmed at 10° C. per minute).

FIG. 5 is the NMR spectrum for the reaction product which containscompounds having the structures: ##STR99##

FIG. 5 is the infrared spectrum for the reaction product containingcompounds having the structures: ##STR100##

FIG. 7 is the NMR spectrum for the reaction product having thestructures: ##STR101##

FIG. 8 is the infrared spectrum for the reaction product having thestructures: ##STR102##

FIG. 9 is the NMR spectrum for the reaction product having compoundshaving the structures: ##STR103##

FIG. 10 is the infrared spectrum of the reaction product containingcompounds having the structures: ##STR104##

FIG. 11 is the NMR spectrum for that fraction of the reaction producthaving compounds having the structures: ##STR105##

EXAMPLE IC PREPARATION OF MIXTURES OF3-METHYL-5-(2,2,3-TRIMETHYL-3-CYCLOPENTENE-1-YL)-3(OR 4)-PENTEN-2-OL AND6-(2,2,3-TRIMETHYL-3-CYCLOPENTENE-1-YL)-4 (OR 5)-HEXENE-3-OL

Reaction ##STR106## wherein one of the dashed lines represents acarbon-carbon double bond and the other of the dashed lines represents acarbon-carbon single bond and one of R₁ or R₂ is methyl and the other ofR₁ or R₂ is hydrogen and M is sodium.

In a 250 ml three-necked reaction flask is placed a solution of 71 gramsof a mixture of 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-3(or4)-pentene-2-one and 6-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4(or5)-hexene-3-one prepared according to Example IB in 80 ml of anhydrousmethanol. To this material is added a solution of 6.5 grams of sodiumborohydride in 20 ml of methanol over a period of 10 minutes whilemaintaining the reaction mixture at 20°-23° C. The reaction mixture isthen stirred at room temperature for a period of 2 hours, and afterstirring 50 ml of a 10% aqueous acetic acid solution is added whilemaintaining the reaction mass at a temperature of about 25° C. Theresulting organic layer is separated from the reaction mass and washedwith saturated sodium bicarbonate solution and saturated sodium chloridesolution. Distillation at 3 mmHg pressure yields 56 grams of a crudeproduct which is redistilled at 2.0 mmHg pressure to obtain 54 grams(76% yield of theory) of pure product having a boiling point 115°-122°C. at 2.0 mmHg pressure.

The fractionation data is as follows:

    ______________________________________                                                                             Fraction                                       Vapor       Liquid      Vac.   weight                                   No.   Temp(°C.)                                                                          Temp(°C.)                                                                          mm Hg  (grams)                                  ______________________________________                                        1     100-114     100-120     2.0    2.6                                      2     114-115     120         2.0    6.1                                      3     115-116     120         2.0    5.2                                      4     116-117     120-122     2.0    5.7                                      5     117         122         2.0    5.5                                      6     117-118     122-123     2.0    6.0                                      7     118-120     123-125     2.0    6.5                                      8     120         125         2.0    6.4                                      9     120         125-130     2.0    6.2                                       10   120-121     130-150     2.0    2.9                                       11   121-122     150-180     2.0    1.2                                      ______________________________________                                    

Preparative GLC yield 6 peaks, designated "A", "B", "C", "D", "E" and"F".

FIG. 13 sets forth the NMR spectrum for peak A.

FIG. 14 sets forth the NMR spectrum for peak B.

FIG. 15 sets forth the NMR spectrum for peak C.

FIG. 16 sets forth the infrared spectrum for peak C.

FIG. 17 sets forth the NMR spectrum for peak D.

FIG. 18 sets forth the infrared spectrum for peak D.

FIG. 19 sets forth the NMR spectrum for peak E.

FIG. 20 sets forth the infrared spectrum for peak E.

FIG. 21 sets forth the NMR spectrum for peak F.

FIG. 22 sets forth the infrared spectrum for peak F.

Peaks A, B, C, D, E and F contain compounds having the structures asfollows: ##STR107##

EXAMPLE IIA PREPARATION OF CAMPHOLENYLIDENE CYCLOHEXANONE

Reaction: ##STR108##

Into a 2 liter autoclave capable of being pressurized to 20 atmospheresare charged 152 grams of (1.0 moles) campholenic aldehyde, 490 grams(5.0 moles) of cyclohexanone and 44 grams (0.2 moles) of zinc acetatedihydrate. The contents of the autoclave are heated to 180° C. and at apressure of 160-170 psig for a period of 10 hours. At the end of the 10hour period, the reaction mass is cooled and solids are filtered andwashed neutral with sodium bicarbonate and aqueous sodium chloride.

The resulting reaction product is distilled through a splash columncontaining saddle stones yielding the following fractions:

    ______________________________________                                              Vapor      Liquid      Vac.   Weight of                                 No.   Temp(°C.)                                                                         Temp(°C.)                                                                          mm Hg  Fraction                                  ______________________________________                                        1     31-94       70-157     3.0    22.7                                      2      94-128    157-168     3.0    5.1                                       3     128-130    168-200     .8     53.5                                      4     130-195    200-227     .8     59.8                                      ______________________________________                                    

53.5 grams of product is collected. The GLC profile for this product isset forth in FIG. 23. Fraction 3 resulting from the fractionaldistillation has a GLC profile as set forth in FIG. 24. The NMR spectrumfor fraction 3 is set forth in FIG. 25. Fraction 3 contains the isomers:##STR109##

EXAMPLE IIB PREPARATION OF CAMPHOLENYLDIENE CYCLOHEXANOL

Reaction: ##STR110##

In a 250 ml three-necked reaction flask is placed a solution of 52 gramsof campholenylidene cyclohexanone, fraction 3 according to Example IIA(0.22 moles) in 50 ml of anhydrous methanol. To this solution 3.5 grams(0.092 moles) of sodium borohydride dissolved in 20 ml of anhydrousmethanol is added over a period of 30 minutes while maintaining thereaction mixture at 20°-23° C. The reaction mass is then stirred at roomtemperature for a period of 4 hours. 10% acetic acid is added dropwise(100 ml) over a period of 5 minutes at about 15° C. The reaction mass isthen stirred for another 10 minutes and the aqueous layer is separatedfrom the organic layer. The organic layer is washed with 100 ml 10%acetic acid and washed neutral with saturated sodium bicarbonate. Thereaction mass is then distilled on a micro-vigreaux column yielding thefollowing fractions:

    ______________________________________                                                Vapor      Liquid     Vac.   Wt. of                                   No.     Temp(°C.)                                                                         Temp(°C.)                                                                         mm Hg  Fraction                                 ______________________________________                                        1       121-135    149-149    3      2                                        2       135-143    149-158    3      14.9                                     3       143        158-162    3      11.8                                     4       143        162-173    3      7.1                                      5       143        173-230    3      6                                        ______________________________________                                    

FIG. 26 is the GLC profile for fraction 2 of the reaction product.

FIG. 27 is the NMR spectrum for fraction 2.

Fraction 2 contains the following compounds having the structures:##STR111##

EXAMPLE IIIA PREPARATION OF ALPHA-CAMPHOLENYLIDENE ACETONE

Reaction: ##STR112## wherein one of the dashed lines is a carbon-carbonsingle bond and the other of the dashed lines is a carbon-carbon doublebond.

Into a 2 liter autoclave equipped with heater and stirrer are placed 76grams (0.5 moles) of campholenic aldehyde, 290 grams (5.0 moles) ofacetone and 22 grams (0.1 moles) of zinc acetate dihydrate. Theautoclave is sealed and heated at a temperature of 180° C. for 10 hourswherein the pressure rises and is maintained at between 320 and 340psig. At the end of the 10 hour period the autoclave contents are cooledand filtered through Supercel. The filtrate is washed with 100 mlsaturated sodium chloride solution and the crude is distilled (rushedover) through a "micro distillation column" yielding the followingfracctions:

    ______________________________________                                                Vapor      Liquid     Vac.   Wt. of                                   No.     Temp(°C.                                                                          Temp(°C.)                                                                         mm Hg  Fraction                                 ______________________________________                                        1       31-33      42-82      30     4.5                                      2       33-45       82-110    30     4.9                                      3       45-68      110        2.5    5.0                                      4        68-104    110-118    3.0    18.4                                     5       104-108    118-125    3.0    13.4                                     6       108        128-142    3.0    14.3                                     7       108-118    142-182    3.0    7.0                                      8       118-137    182-205    2.0    2.3                                      ______________________________________                                    

The reaction product is then subjected to gas liquid chromotography andthe GLC profile exists in two major peaks, peak A and peak B. The NMRspectrum for peak A is set forth at FIG. 28. The infrared spectrum forpeak A is set forth in FIG. 29. The NMR spectrum for peak B is set forthin the FIG. 30. The IR spectrum for peak B is set forth in FIG. 31. PeakA contains compounds having the structures: ##STR113## and has thefollowing NMR assignments:

    ______________________________________                                         ##STR114##                                                               

    ______________________________________                                        a-2.10 ppm   (s)                                                                                           6H                                               e,f-2.10     (m)                                                              b-3.14       (d)             2H                                               c,d-5.59     (m)             2H                                               g-5.23       (broad)         1H                                               h-1.59       (allylic        3H                                                             coupling)                                                       i,j-0.98,    (2 singlets)    6H                                               0.78                                                                          ______________________________________                                    

Peak B contains compounds having the structures: ##STR115## and has thefollowing NMR assignments:

    ______________________________________                                         ##STR116##                                                               

    ______________________________________                                        a-2.20 ppm   (s)                                                              d,e,f-1.75- 2.0                                                                            (m)       8H                                                     b,c-5.8-7.0  (m)       2H                                                     g-5.35       (broad)   1H                                                     h-1.59       (allylic  3H                                                                   coupling)                                                                              3H                                                     i,j-0.98,0.78                                                                              (2 singlets)                                                                            6H                                                     ______________________________________                                    

EXAMPLE IIIB PREPARATION OF5(2,2,3-TRIMETHYL-3-CYCLOPENTEN-1-YL)-3-PENTEN-2-OL

Reaction: ##STR117## wherein one of the dashed lines is a carbon-carbonsingle bond and the other of the dashed lines is a carbon-carbon doublebond and wherein M is sodium.

Into a 250 ml reaction flask equipped with stirrer thermometer refluxcondenser are placed fractions 4, 5 and 6 resulting from thedistillation of the reaction product of Example IIIA (46 grams or 0.24moles); a mixture of ketones having the structures: ##STR118## dissolvedin 50 ml anhydrous methanol. To this solution is added a solution of 4.6grams (0.12 moles) of sodium borohydride dissolved in 15 ml anhydrousmethanol over a period of 8 minutes while maintaining the reaction massat a temperature of 25°-40° C. The reaction mass is then stirred at13°-19° C. for a period of one hour. The reaction mass is thenmaintained for a period of 12 hours at room temperature. At the end ofthe 12 hour period 50 ml 10% acetic acid solution is added whilemaintaining the reaction temperature at 5° C. The resulting organiclayer is then washed with saturated sodium bicarbonate followed bysaturated sodium chloride solution. The resulting product is thendistilled yielding the following fractions:

    ______________________________________                                                Vapor      Liquid     Vac.   Wt. of                                   No.     Temp(°C.)                                                                         Temp(°C.)                                                                         mm Hg  Fraction                                 ______________________________________                                        1       95-98      107-112    2      2.3                                      2        98-106    112-117    2      5.7                                      3       160-110    117-120    2      8.8                                      4       110        120        2      6.2                                      5       110-112    120-147    2.7    7.2                                      6       112-98     147-144    2.6    3.7                                      ______________________________________                                    

The total weight of product is 31.6 grams.

The GLC profile contains two major peaks, peak A and peak B. FIG. 32 isthe NMR spectrum for peak A. FIG. 33 is the NMR spectrum for peak B.FIG. 34 is the infrared spectrum for peak B. Peak A is given thefollowing NMR assignments:

    ______________________________________                                         ##STR119##                                                               

    ______________________________________                                        a-1.15 ppm   (d)        3H                                                    b-4.1        (m)       1                                                      c-3.4        (d)       1                                                      d,e-5.5      (m)       2                                                      f,g,h-1.9    (m)       5                                                      i-5.15       (m)       1                                                      j-1.55       (allylic  3                                                                    coupling)                                                       k,l 0.80,0.95                                                                              (singlets)                                                                              6                                                      ______________________________________                                    

The NMR assignments for peak B are as follows:

    ______________________________________                                         ##STR120##                                                               

    ______________________________________                                        a-1.1 ppm    (d)       3H                                                     k,l-0.75,0.94                                                                              (singlets)                                                                              6H                                                     j-1.55       (allylic  3H                                                                   coupling)                                                       d,g,h-2.15   (m)       5H                                                     c-3.25       (d)       1H                                                     b-3.7        (m)       1H                                                     i-5.15       (m)       1H                                                     e,f-5.47     (m)       2H                                                     ______________________________________                                    

EXAMPLE IVA PREPARATION OF6(2,2,3-TRIMETHYL-3-CYCLOPENTEN-1-YL)-4-METHYL-4 (AND 5) HEXEN-3-ONES

Reaction: ##STR121##

Into an autoclave are charged the following ingredients:

Campholenic aldehyde (76 grams; 0.5 moles)

3-pentanone (430 grams; 5.0 moles)

Zinc acetate dihydrate (22 grams; 0.1 moles)

The autoclave is sealed and heated to 190° C. for a period of 10 hoursmaintaining the pressures thereof at 160-185 psig. After cooling, solidsin the reaction mass are filtered and the crude product is washedneutral with saturated sodium bicarbonate and saturated sodium chloride.After the recovery of unreacted 3-pentanone, the reaction mass productresidue is distilled under 3 mm Hg pressure yielding 78.8 grams of crudeproduct.

Redistillation using a 6 inch micro-vigreux column yielded the followingfractions:

    ______________________________________                                                Vapor      Liquid     Vac.   Wt. of                                   No.     Temp (°C.)                                                                        Temp.(°C.)                                                                        mm Hg  Fraction                                 ______________________________________                                        1       25-58                 3      1.4                                      2       58         97         3      6.8                                      3       58-73       97-121    3      1.9                                      4        73-109    121-130    2.8    11.5                                     5       109-118    130-133    2.8    8.1                                      6       118-119    133        2.8    12.7                                     7       119        133-134    2.8    7.3                                      8       119        134        2.8    13.2                                     9       119-123    134-135    2.8    8.4                                      10      123        135-136    2.8    5.9                                      11      123-124    136-187    2.8    .5                                       ______________________________________                                    

FIG. 35 is the GLC profile for bulked fractions 4-11. The two majorpeaks represent compounds having the following structures: ##STR122##

FIG. 36 is the NMR spectrum for peak A of the reaction product producedaccording to Example IVA containing compounds having the structures:##STR123##

FIG. 37 is the infrared spectrum for peak A of the reaction productproduced according to Example IVA.

FIG. 38 is the NMR spectrum for the reaction product of Example IVA peakB.

FIG. 39 is the infrared spectrum for peak B of the reaction product ofExample IVA containing the compounds: ##STR124##

EXAMPLE IVB PREPARATION OF 6-(2,2,3-TRIMETHYLCYCLOPENTEN-1YL)-4-METHYL-4(AND 5) HEXEN-3-OL

Reaction: ##STR125## wherein one of the dashed lines is a carbon-carbonsingle bond and the other of the dashed lines is a carbon-carbon doublebond and M is sodium.

Into a 150 ml flask equipped with stirrer, thermometer, reflux condenserand heating mantle are placed 5.7 grams (0.15 moles) of sodiumborohydride in 10 ml of anhydrous isopropanol. The ketone reactionproduct (fractions 4-11 resulting from the fractionation) producedaccording to Example IVA (66.5 grams; 0.3 moles) admixed with 70 mlisopropyl alcohol is then added to the sodium borohydride isopropylalcohol solution while maintaining the temperature thereof at 7°-10° C.The reaction mass is then stirred at a temperature of between 7° and 26°C. for a period of 9.5 hours. At the end of the 9.5 hour period thereaction mass is quenched with a 10% aqueous acetic acid solution (50ml) while maintaining the temperature at 0° C. The reaction mass is thenwashed neutral with aqueous sodium bicarbonate followed by aqueoussodium chloride and then distilled yielding the following fractions:

    ______________________________________                                              Vapor       Liquid             Wt. of                                   No.   Temp. (°C.)                                                                        Temp. (°C.)                                                                        Vac.   Fraction                                 ______________________________________                                        1      90-125     130-133     2.5-2.2                                                                              1.6                                      2     112-126     133         2.2    3.8                                      3     126         133-134     2.2    5.4                                      4     126-127     134-135     2.2    5.0                                      5     127-128     135         2.2    5.8                                      6     128         135-137     2.2    6.3                                      7     128         137-138     2.2    6.8                                      8     128-129     138-140     2.2    6.3                                      9     129-130     140-160     2.2    6.6                                      10    130         160-175     2.2    0.4                                      ______________________________________                                    

The reaction mass is then analyzed using GLC (carbowax 10 ft.×1/4 inchcolumn at 220° C., isothermal) and NMR, IR, mass spectral analyses yieldthe information that the resulting product has the structures:##STR126## as well as a compund having the structure: ##STR127##according to the GLC profile the reaction mass contains 21% by weight ofcompounds having the structures: ##STR128## 62.0% by weight of compoundshaving the structures: ##STR129## and 14.0% by weight of compound havingthe structure: ##STR130## The GLC profile is set forth in FIG. 40wherein peak A and peak B are for compounds having the structures:##STR131## and peak C is for compound having the structure: ##STR132##and peak D is for compounds having the structures: ##STR133##

FIG. 41 is the NMR spectrum for peak D containing compounds having thestructures: ##STR134##

EXAMPLE VA PREPARATION OF CAMPHOLENYLIDENE CYCLOPENTANONE

Reaction: ##STR135## wherein one of the dashed lines is a carbon-carbonsingle bond and the other of the dashed lines is a carbon-carbon doublebond.

Into an autoclave are charged the following ingredients:

Campholenic aldehyde (76 grams:0.5 moles)

Cyclopentanone (425 grams; 5.0 moles)

Zinc acetate dihydrate (22 grams; 0.1 moles)

The autoclave is sealed and heated to 190° C. for a period of 10 hoursmaintaining the pressures thereof at 160-185 psig. After cooling, thesolids in the reaction mass are filtered and the crude product is washedneutral with saturated sodium bicarbonate and saturated sodium chloride.After recovery of unreacted cyclopentanone, the reaction mass productresidue is distilled under 3 mm Hg pressure. Redistillation using a 6inch micro-vigreux column yielded the following fractions:

    ______________________________________                                                 Vapor        Liquid       Vac.                                       No.      Temp. (°C.)                                                                         Temp (°C.)                                                                          mm Hg                                      ______________________________________                                        1        105-105      155-169      4.8                                        2        125          155          2.5                                        3        132          161          1.2                                        4        170          161          1.8                                        5        203          170          1.8                                        ______________________________________                                    

FIG. 42 is the NMR spectrum for the reaction product of this Examplecontaining compounds having the structures: ##STR136##

FIG. 43 is the infrared spectrum for the reaction product of thisExample containing compounds having the structures: ##STR137##

EXAMPLE VB PREPARATION OF CAMPHOLENYLIDENE CYCLOPENTANOL

Reaction: ##STR138## wherein one of the dashed lines is a carbon-carbonsingle bond and the other of the dashed lines is a carbon-carbon doublebond and M is sodium.

Into a 150 ml flask equipped with stirrer, thermometer, reflux condenserand heating mantle are placed 1.52 grams (0.04 moles) of sodiumborohydride in 20 ml of anhydrous isopropanol. The ketone reactionproduct (fractions 3, 4 and 5 resulting from the fractionation) producedaccording to Example VA (21 grams; 0.1 moles) is then added to thesodium borohydride/isopropyl alcohol solution while maintaining thetemperature at 20° C. The reaction mass is then stirred at roomtemperature for a period of 8 hours. At the end of the 8 hours periodthe reaction mass is quenched with 10% aqueous acetic acid solution (25ml). The reaction mass is then washed neutral with aqueous sodiumbicarbonate followed by toluene in order to aid separation. The reactionmass is then microdistilled at 124° C. vapor temperature (144° C. liquidtemperature) at 2.2 mm Hg pressure yielding 33 grams of reaction productcontaining compounds having the structures: ##STR139##

FIG. 44 is the NMR spectrum for the reaction product of Example VBcontaining compounds having the structures: ##STR140##

FIG. 45 is the infrared spectrum for the reaction product of Example VBcontaining compounds having the structues: ##STR141##

EXAMPLE VI

The following four synthetic sandalwood oil formulations are produced:

    ______________________________________                                        Ingredient        VIA     VIB     VIC   VID                                   ______________________________________                                        Amyrus Oil        100     100     100   100                                   Amyrus Acetate    220     220     220   220                                   Cedarwood Oil     150     150     150   150                                   Trans decahydro beta-naphthol                                                                   100     100     100   100                                   Formate                                                                       Guaiophene (1% in diethyl                                                                       50      50      50    50                                    phthalate)                                                                    Eugenol (10% in diethyl                                                                         50      50      50    50                                    phthalate)                                                                    Galaxolide® (2.5% in diethyl                                                                30      30      30    30                                    phthalate                                                                     Geranyl Phenyl Acetate                                                                          50      50      50    50                                    Mixture of generic compounds                                                  defined by the generic                                                        structure                                                                      ##STR142##                                                                   (wherein one of the dashed lines                                                                250                                                         is a carbon-carbon single bond                                                and the other of the dashed                                                   lines is a carbon-carbon double                                               bond and one of R.sub.1 or R.sub.2 is                                         methyl and the other of R.sub.1 or                                            R.sub.2 is hydrogen) produced accord-                                         ing to Example IC.                                                            Mixture of compounds      250                                                 having the structures:                                                         ##STR143##                                                                    ##STR144##                                                                    ##STR145##                                                                   produced according to Example                                                 IIB                                                                           Mixture of compounds              250                                         having the structures:                                                         ##STR146##                                                                    ##STR147##                                                                    ##STR148##                                                                    ##STR149##                                                                   produced according to Example                                                 IIIB                                                                          Mixture of compounds each of which      250                                   is defined within the                                                         genus having the structure:                                                    ##STR150##                                                                   wherein one of the dashed lines is                                            a carbon-carbon single bond and                                               the other of the dashed lines is                                              a carbon-carbon double bond and                                               wherein one R.sub.1 or R.sub.2 is methyl and                                  the other of R.sub.1 or R.sub.2 is hydrogen                                   produced according to Example IB.                                             ______________________________________                                    

The addition of 25% of the 2,2,3-trimethyl-3-cyclopentene-1-ylalkenyland alkylidene secondary alkanols, alkanones and cycloalkanols to thesandalwood formulation contributes the main sandalwood note to thefragrance. The odor of the fragrance in each of the cases VIA, VIB, VICand VID without said 2,2,3-trimethyl-3-cyclopentene-1-ylalkenyl andalkylidene secondary alkanols, alkanones and cycloalkanols is fardistant from the desired odor of sandalwood.

EXAMPLE VII SANDAL PERFUME FORMULATION

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        1',2',3',4',5',6',7',8'-octahydro-                                                                  540                                                     2',3',8',8',-tetramethyl-2'-aceto-                                            naphthone isomer mixture produced                                             according to the process of Example                                           VII of Application for U.S. Letters                                           Pat. No. 434,948 filed on                                                     January 21, 1974 (now U.S. Pat.                                               No. 3,911,018 issued on October 7,                                            1975).                                                                        Cedrenal - (A tricyclic sesquiterpinic                                                              90                                                      aldehyde derived from cedrene, having                                         the structure:                                                                 ##STR151##                                                                   produced according to the process of                                          U.S. Pat. Application 260,537 filed                                           on June 7, 1972 (now U.S. Pat. No.                                            3,869,516, issued on March 4, 1975)                                           (corresponding to published Dutch                                             Appln. 7,307,849 laid open for public                                         inspection on December 11, 1973).                                             Eugenol (1% in ethyl alcohol)                                                                       54                                                      2,5,5-trimethyl acetyl cycloheptane                                                                 180                                                     produced according to Example I of                                            U.S. Pat. Application 349,180                                                 filed on April 9, 1973 (now U.S.                                              Pat. No. 3,869,411 issued on                                                  March 4, 1975).                                                               Borneol (1% in ethyl alcohol)                                                                       18                                                      Hexahydro-4,7-methanoindane-2-                                                                      18                                                      carboxaldehyde                                                                Mixture of compounds having the                                                                     100                                                     structures:                                                                    ##STR152##                                                                    ##STR153##                                                                    ##STR154##                                                                   produced according to Example                                                 VB.                                                                           ______________________________________                                    

The mixture of compounds produced according to Example VB imparts thewoody, sandalwood-like note to the instant formulation, also lending toit some "cyclamal®-like" and "lilial®-like character".

EXAMPLE VIII PREPARATION OF A SOAP COMPOSITION

A total of 100 grams of soap chips produced from unperfumed sodium basetoilet soap made by tallow and coconut oil are mixed with 1 gram of theperfume composition produced according to Example VIA until asubstantially homogeneous composition is obtained. The soap compositionmanifests a characteristic "sandal cologne" aroma having intense muskynuances. Similar sandal cologne aroma containing soaps are producedusing the compositions of Examples VIB, VIC, VID and VII.

EXAMPLE IX PREPARATION OF A SOAP COMPOSITION

A total of 100 grams of soap chips produced from unperfumed sodium basetoilet soap made from tallow and coconut oil is mixed with 1 gram of amixture of compounds defined by the generic structures: ##STR155##wherein one of the dashed lines is a carbon-carbon single bond and theother of the dashed lines is a carbon-carbon double bond and one of R₁or R₂ is methyl and the other of R₁ or R₂ is hydrogen produced accordingto Example IC until a substantially homogeneous composition is obtained.The soap composition manifests a powerful sandalwood aroma with nuttyand oily nuances and also have an intense musky topnote.

EXAMPLE X PREPARATION OF A SOLID DETERGENT COMPOSITION

A total of 100 grams of a detergent powder sold under the trademark"RINSO"® are mixed with 0.15 grams of a perfume composition containingthe mixture of Example III until a substantially homogeneous compositionhaving a "sandal cologne" fragrnce with woody notes and a"cyclamal-lilial" character is obtained.

EXAMPLE XI PREPARATION OF COLOGNE AND HANDKERCHIEF PERFUME

The composition of Example III is incorporated into a cologne having aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume in a concentration of 20% (in 95% ethanol). The use of thecomposition of Example III affords a distinct and definite "sandalcologne" aroma having a warm sandalwood-like character to thehandkerchief perfume and to the cologne.

EXAMPLE XII PREPARATION OF COLOGNE AND HANDKERCHIEF PERFUME

A mixture of compounds defined by the generic structure: ##STR156##wherein one of the dashed lines is a carbon-carbon single bond and theother of the dashed lines is a carbon-carbon double bond and one of R₁or R₂ is methyl and the other of R₁ or R₂ is hydrogen produced accordingto Example IC is incorporated into colognes having concentrations of2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and 5.0% in 85% aqueous foodgradeethanol; and into handkerchief perfumes in concentrations of 15%, 20%,25%, 30% and 35% (in 95% foodgrade ethanol). The uses of the mixture ofcompounds defined by the generic structure: ##STR157## producedaccording to Example IC afford a distinct and definite sandalwood aromawith nutty and oily nuances and intense musky topnotes to thehandkerchief perfumes and to the colognes prepared as above.

EXAMPLE XIV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with strong cedarwood and sandalwoodaromas are prepared containing 0.10%, 0.15% and 0.20% of a mixture ofcompounds having the structures: ##STR158## prepared according toExample IIB. The liquid detergents are prepared by adding andhomogeneously mixing the appropriate quantity of said mixture ofcompounds prepared according to Example IIB in the liquid detergentdescribed according to British Pat. No. 1,092,149 containing 2% byweight ethyl/maleic anhydride copolymer (specific viscosity 0.5-1.0) and0.42 weight percent methyl vinyl ethyl/maleic anhydride copolymer(specific viscosity 0.4) as stabilizer and 8% by weight of a sultainedetergent. The detergents all possess strong cedarwood, sandalwood aromswith sweet nuances, the intensity increasing with greater concentrationof compounds prepared according to Example IB. A similar effect isobtained using the separate constituents of the composition preparedaccording to Example IIB with these detergents.

EXAMPLE XV PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (essentially water solublenon-ionic detergent and stable laundry enzyme as described in U.S. Pat.No. 3,953,353 issued on Apr. 27, 1976) is mixed with 0.15 grams ofcompound defined by the structure: ##STR159## until a substantiallyhomogeneous composition is obtained. This composition has an excellentfloral ionone violets-like aroma with fatty rue oil nuances.

EXAMPLE XVI PREPARATION OF A SOAP COMPOSITION

A marble soap is prepared according to British Pat. No. 1,507,705 issuedon Apr. 19, 1978 producing 0.15 grams of the compound having thestructure: ##STR160## into 100 grams of soap just prior to extrusion.After manufacture the soap possesses a pleasant fruity, ionony, green,buttery, aroma.

What is claimed is:
 1. A compound having the structure: ##STR161##wherein m is 0 or 1; wherein one of the lines ++++ is a carbon-carbonsingle bond and the other of the lines ++++ is a carbon-carbon doublebond and wherein X is carbinol having the structure: ##STR162##
 2. Thecompound of claim 1 wherein X is carbinol having the structure:##STR163## and n is
 1. 3. The compound of claim 1 wherein X is carbinolhaving the structure: ##STR164## and m is 0.